Epoxy-acrylic graft polymers

ABSTRACT

Phenoxy terminated epoxy resins are grafted by carbon-carbon graft with ethylenic monomers, including alkylol acrylamide monomer, by in-situ polymerization to produce grafted epoxy-acrylic copolymers useful as binders in protective coatings. The cured paint films exhibit superior resistance to pine oil and limonene derivatives.

This is a continuation-in-part of copending application Ser. No. 859,421filed May 5, 1986, now abandoned, and the same is incorporated herein byreference.

This invention is directed to low acid number epoxy-acrylic graftpolymers and more particularly to phenoxy terminated epoxy polymersgrafted with ethylenic monomers including alkylol acrylamide monomer.

Epoxy resins are particularly desirable for use in surface coatingmaterials as a vehicle or polymeric binder for pigments, fillers, andother additives whereby epoxy resins advantageously provide toughness,flexibility, adhesion, and chemical resistance. Water-dispersed coatingcompositions containing epoxy resins are highly desirable for cancoating compositions. Coatings for soft drink and beer cans, forinstance, are critical due to taste sensitivity wherein such sanitarycan coatings must not alter the product taste of canned beverages. Tasteproblems can occur in a variety of ways such as by leaching of coatingcomponents into the beverage, or by adsorption of flavor by the coating,or sometimes by chemical reaction, or by some combination thereof. Incommonly assigned U.S. Pat. No. 4,212,781, a process is disclosed formodifying epoxy resin by reacting the epoxy resin with additionpolymerizable monomer in the presence of at least 3% by weight ofbenzoyl peroxide (or the free radical initiating equivalent thereof)based on monomer at a suitable reaction temperature. This reactionproduces a reaction mixture containing an in-situ formed blend ofresinous materials comprising an epoxy-acrylic copolymer mixturecontaining epoxy resin, graft epoxy-acrylic polymer, andassociatively-formed ungrafted addition polymer. The in-situ polymerizedmonomers include acid functional monomers to provide acid functionalityin the reaction mixture sufficiently high to effect stable dispersion ofthe resulting reaction product in a basic aqueous medium. In a preferredembodiment of U.S. Pat. No. 4,212,781, a polyglycidyl ether ofbisphenol-A is reacted with a mixture of addition polymerizable monomerscontaining an acrylic such as methacrylic acid. The epoxy resin has amolecular weight above 4,000 and provides from 50% to 90% of the initialreaction mixture. The reaction takes place in the presence of benzoylperoxide at an elevated temperature above 80° C. and preferably betweenabout 110° C. and 130° C. to effect addition polymerization of themonomer and produce addition polymer grafted to the epoxy resin. Thereaction product can be dispersed in a basic aqueous medium to form awater-reducible epoxy-acrylic copolymer mixture.

In commonly assigned U.S. Pat. No. 4,522,961, it was found that certainreactive self-curing water dispersed polymers blended with anepoxy-acrylic copolymer mixture provides an excellent sprayable coatingsuitable for an interior coating for beverage and food containers. Thereactive self-curing water-dispersed polymer contains copolymerizedmonomers including functional carboxyl, hydroxyl, amine, or amidemonomers in combination with alkylol acrylamide monomer. The monomerspreferably are polymerized in a step-wise reaction to concentrate thealkylol acrylamide on the surface of the water dispersed polymerparticles to provide an improved stabilized water-dispersed polymerexhibiting surprisingly good rheological properties including viscosity,stability and spray application. By concentrating alkylol acrylamide onthe polymer surface and by polymerizing at temperatures preferably above70° C., it is believed that a minor amount of alkylol acrylamide reactsand cross-links with a minor amount of functional monomer during theaddition polymerization of ethylenic monomers to provide a relativelyrigid or hard polymer particle surface, which apparently stabilized theviscosity of the water-dispersed blend as well as provide considerableshear resistance during subsequent spray application of the polymericblend. By blending the reactive self-curing water-dispersed polymer witha water-dispersed epoxy-acrylic copolymer, the blend provides anexcellent sprayable interior coating particularly suitable for beveragecans. A preferred polymeric blend comprises an aqueous dispersedphosphated polymer blended with the reactive self-curing latex polymerand the epoxy-acrylic copolymer.

In commonly assigned U.S. Pat. No. 4,499,212 a sprayable latex polymerproduced by step-wise copolymerization of ethylenic monomers, includingalkylol acrylamide monomer, functional monomer, and other ethylenicmonomers are copolymerized in water to produce a self-curing latexcopolymer.

U.S. Pat. No. 4,355,122 discloses water-dispersed high molecular weightphenoxy resins derived from diphenols and epichlorohydrin.

It now has been found that phenoxy terminated epoxy resins grafted withethylenically unsaturated monomers, including at least one alkylolacrylamide monomer, by in-situ polymerization in the presence of atleast 3% by weight peroxide catalyst to provide a carbon-to-carbon graftwith epoxy polymer provides an excellent low acid number self-curingepoxy-acrylic copolymer. The composition can be readily dispersed intowater even though the Acid No. is below 30 and advantageously provides asmall particle size polymeric dispersion useful as a water dispersedcoating particularly useful as interior coatings for food and beveragecontainers. These and other advantages of this invention will becomemore apparent from the detailed description of the invention and theillustrative examples.

SUMMARY OF THE INVENTION

Briefly, the composition comprises a high molecular weight, low acidnumber epoxy polymer grafted with copolymerized ethylenicallyunsaturated monomers by carbon-to-carbon graft to the epoxy polymerbackbone to produce an epoxy-acrylic graft copolymer. The composition isproduced by copolymerizing the ethylenic monomers, including alkylolacrylamide monomer, in the presence of epoxy polymer by in situpolymerization where at least 3% peroxide initiator based on the weightof monomers to produce an in-situ formed mixture of carbon-to-carbongraft epoxy-acrylic copolymer, ungrafted acrylic copolymer, andungrafted epoxy resin.

DETAILED DESCRIPTION OF THE INVENTION

The polymeric composition of this invention comprises epoxy polymergrafted with copolymerized ethylenic monomers including alkylolacrylamide monomers.

Referring first to the epoxy resin, the epoxy can be either aliphatic oraromatic, although the aromatic epoxy resins are preferred. The mostpreferred epoxy resins are polyglycidyl ethers of bisphenol-A, producedfrom excess equivalents of bisphenol-A to provide a phenoxy terminatedepoxy resin. The molecular weight of epoxy resins should be from about350 to about 40,000, and preferably, for sanitary coating compositions,from about 4,000 to about 40,000 number average molecular weight. Inproducing the phenoxy terminated epoxy resins, mixtures of monoepoxidesand diepoxides can be reacted with phenoxy although minor amounts of thearomatic polyether can be devoid of oxirane functionality by reactingepoxide groups with benzoic acid, phenol or similar monoreactive epoxideblocking agent.

While it is sometimes convenient to use a finished epoxy resin at thedesired molecular weight, it is often more practical to start withbisphenol A and the bis-glycidyl ether of bisphenol A, which isavailable from commercial sources. The bisglycidyl ether of bisphenol A,known generally as low molecular weight liquid epoxy resin, is availablein precatalyzed form from Dow Chemical Co. under the trade name DER-333,which contains as a catalyst the complex of ethyl triphenyl phosphoniumacetate with acetic acid. Other commercial epoxy resins are commerciallyavailable from Shell Chemical Co. under the trade name Epon 829 and Epon828, etc.

The precatalyzed liquid epoxy resin from Dow Chemical Co., DER-333, hasthe following physical properties:

                  TABLE I                                                         ______________________________________                                        Properties of DER-333 Epoxy Resin                                             ______________________________________                                        Appearance           Clear, viscous liquid                                    Color (Gardner)      1-2                                                      Specific gravity     1.15                                                     Weight per gallon    9.65                                                     Nonvolatile by weight                                                                              96 ± 1%                                               Volatile             Xylene                                                   Nonvolatile by volume                                                                              95% avg.                                                 Viscosity at 25° C.                                                                         2300-2400 cps                                            Epoxide equivalent weight*                                                                         199-202                                                  ______________________________________                                         *Epoxide equivalent weight is the grams of resin containing one gram          equivalent weight of epoxy.                                              

To increase the initial molecular weight of a low molecular weightliquid epoxy resin to a level that is more satisfactory for many coatingapplications, the initial liquid epoxy resin can be reacted withadditional bisphenol A or other bisphenol compounds. Otherpolyfunctional aromatic alcohols can be used to make the glycidyl ethersuch as described in U.S. Pat. No. 4,212,781 and is incorporated hereinby reference.

The ratio of bisphenol-A to low molecular weight, liquid epoxy resincoreacted in accordance with this invention to produce a phenoxyterminated epoxy resin determines the epoxy molecular weight as well aswhether the higher molecular weight epoxy resin is epoxide terminated orphenoxy terminated. The weight ratio of bisphenol-A between 0.1 and 0.56per one weight part DER-333 for instance will produce an epoxideterminated epoxy polymer. Weight ratio of bisphenol-A between 0.6 and0.9 per one weight part of DER-333 for instance will produce a phenoxyterminated epoxy polymer. As a generalization, excess equivalents ofbisphenol-A relative to lesser epoxide equivalents of the lowermolecular weight epoxy resin (biglycidyl ether of bisphenol-A) producesa phenoxy terminated epoxy polymer in accordance with this invention. Incontrast, a deficiency of equivalents of bisphenol-A produces an epoxideterminated epoxy polymer outside the scope of this invention.

For many coating applications, the epoxy resin can have a molecularweight in the range from about 350 to about 40,000 and desirably between350 and 20,000 based on number average. However, for more demandingapplications, particularly for applications where the end product is tobe a sanitary coating, epoxy resin molecular weight values in the rangefrom about 4,000 to about 40,000 are preferred. These and othermolecular weight determinations of the epoxy resin components can bemade by oxirane value titration but preferably are made by gelpermeation chromatography (GPC).

Epoxy resins include epoxy derivatives such as phenoxy terminated resinscomprising substantially linear polymers of the general formula:##STR1## where n=30 to 80 or more. The phenoxy resins can includemixtures of two or more thermoplastic polyhydroxyethers derived fromdiphenols and epichlorohydrin.

Referring next to ethylenically unsaturated monomers, such monomerscontain carbon-to-carbon unsaturation and include generally vinylmonomers, acrylic monomers, acrylamide and allylic monomers. Thealkylated alkylol acrylamide monomers can be derivatives of acrylamide,methacrylamide, methylol acrylamide, or similar alkyl modifiedacrylamide monomer as shown for example in U.S. Pat. No. 3,991,216; U.S.Pat. No. 4,097,438; and U.S. Pat. No. 4,305,859. The acrylamide monomerspreferably are alkylated with an alkyl group such as methyl, ethyl,propyl, n-butyl, or iso-butyl, and similar alkylated alkylol acrylamidemonomers, wherein the butylated monomers are preferred. Functionalmonomers include carboxyl or hydroxyl functional group containingmonomers. Carboxy containing monomers include acrylic acid and loweralkyl substituted acrylic acids wherein the preferred carboxylicmonomers are acrylic and methacrylic acids. Hydroxyl containing monomersare hydroxy containing ethylenically unsaturated monomers includinghydroxy alkyl acrylates such as 2-hydroxy ethyl acrylate andmethacrylate, 2-hydroxy-propyl acrylate and methacrylate, and similarhydroxy alkyl acrylates. On a weight basis, the ethylenicallyunsaturated monomers can comprise between 1% and 25% alkylated alkylolacrylamide monomer and between 1% and 35% functional monomer.

The remaining other ethylenically unsaturated monomers that can becopolymerized with the alkylol acrylamide monomer and functionalmonomers to form the reactive water dispersed polymer, compriseethylenic double bond unsaturated monomers including vinyl, vinylidene,acrylic, allylic and unsaturated mono or dicarboxylic acids. Vinylmonomers include, for example, vinyl esters such as vinyl acetate, vinylproprionate, vinyl butyrates, vinyl benzoate, isopropenyl acetate andsimilar vinyl esters; and vinyl halides such as vinyl chloride. Vinylaromatic hydrocarbon monomers can include, for example, styrene, methylstryenes, and similar alkyl styrenes, chlorostyrene, vinyl toluene,vinyl naphthalene, divinyl benzene, diallyl phthalate and similardiallyl derivatives. Vinyl aliphatic monomers include olefinicunsaturated monomers such as butadiene, substituted butadienes,cyclopentadienes, dicyclopentadiene, cyclohexene, and vinyl naphthalene.Acrylic monomers include monomers such as lower alkyl esters of acrylicor methacrylic acid having an alkyl ester portion containing between 1to 12 carbon atoms as well as aromatic derivatives of acrylic andmethacrylic acid. Useful acrylic monomers include, for example, acrylicand methacrylic acid, methyl acrylate and methacrylate, ethyl acrylateand methacrylate, butyl acrylate and methacrylate, propyl acrylate andmethacrylate, 2-ethyl hexyl acrylate and methacrylate, cyclohexylacrylate and methacrylate, decyl acrylate and methacrylate,isodecylacrylate and methacrylate, benzyl acrylate and methacrylate, andvarious reaction products such as butyl, phenyl, and cresyl glycidylethers reacted with acylic and methacrylic acids, hydroxyl alkylacrylates and methacrylates such as hydroxyethyl and hydroxypropylacrylates and methacrylates, as well as amino acrylates andmethacrylates.

In accordance with this invention, the preferred graft epoxy-acryliccopolymer mixture is prepared by in-situ polymerization of the ethylenicmonomers with epoxy resin and in the absence of water. The epoxy resincan be heated in a reactor wherein the polymerizable monomer can beadded slowly over a period of at least two or three hours along with asolvent and a free radical initiator. Although the reaction may beconducted in the absence of solvent, a solvent system is preferred forthe in-situ polymerization of monomers in the presence of epoxy resin. Apreferred solvent system comprises two miscible solvents, one of whichdissolves the epoxy resin and the other of which dissolves the monomers.The particular solvents satisfactory for the epoxy resin are solventssuch as xylene, benzene, ethyl benzene, toluene, and the alkoxyalkanols. For the monomer, alcohols such as methanol, ethanol, propanol,butanol, and the like, are suitable with butanol being preferred.Ethylene glycol monobutyl ether, ethylene glycol monobutyl etheracetate, and the like, hexane, mineral spirits, and the like, are alsosuitable. For subsequent dispersion into water, the solvents selectedshould be water-soluble materials, as are acetone, butanol, ethanol,propanol, ethylene glycol monoethyl ether, and the like. Ordinarily theamount of solvent may be in the range from about 5% to 30% by weight ofthe sum of the other components. In practice, the epoxy resin and themixture of polymerizable monomers are reacted together in the presenceof a free radical initiator, preferably of the peroxide type, andbenzoyl peroxide is most preferred. Typical and useful free radicalinitiators include cumene hydroperoxide, benzoyl peroxide, t-butylperbenzoate, t-butylperoxide, lauroyl peroxide, methyl ethyl ketoneperoxide, chlorobenzoyl peroxide, and the like. Benzoyl peroxide ispreferred as the free radical initiator for use in the practice of thepresent invention. The amount of free radical catalyst is expressed interms of percentage by weight of benzoyl peroxide based on the totalweight of the polymerizable monomer, or equivalent, at the temperatureof use. The amount of catalyst should be at least 3%, and preferablymore than 4% by weight of benzoyl peroxide or equivalent based onmonomer weight. The reaction temperature preferably is maintained in therange from about 80° C. to about 130° C., although the temperature maybe adjusted within a relatively wide range to accomodate the reactivityof the mixture. Thus, operating temperatures in the range from about 30°C. to about 200° C. are feasible, depending upon the end results andoperating conditions selected. After the monomers are added, thereaction mixture is normally held for up to three hours at reactiontemperature to complete the monomer conversions.

The foregoing in-situ formed mixture comprising graft epoxy polymer,ungrafted acrylic copolymer, and ungrafted epoxy polymer is produced byreacting on a weight basis between 10 and 100 weight parts of ethylenicmonomer including alkylol acrylamide monomer per 100 weight parts ofepoxy polymer. The foregoing in-situ formed epoxy-acrylic copolymermixture can then be combined with an aminoplast cross-linking resincomponents on a polymer solids weight basis between 1 and 40 weightparts cross-linking resin per 100 weight parts of in-situ formedepoxy-acrylic copolymer.

Aminoplast resins are melamine or melamine derivatives and the reactionproduct of ureas and melamines with aldehydes and in some instancesfurther etherified with alcohol such as methylol melamine or similaralkylated melamine formaldehyde resins. Aminoplasts further includebenzoguanamine, acetoguanamine, as well as ureaformaldehyde.Commercially available aminoplasts which are water-soluble orwater-dispersible for the instant purpose include Cymel 301, Cymel 303,Cymel 325, Cymel 325, Cymel 370, and Cymel 373 (all being products ofAmerican Cyanamid, Stamford, Conn., said aminoplasts being melaminebased, e.g., hexamethoxy-methyl melamine for Cymel 303), and Beettle 80products of American Cyanamid which are methylated or butylated ureas.)Other suitable aminoplast resins are of the type produced by thereaction of aldehyde and formal guanamines; ammeline;2-chloro-4,6-diamine-1,3,5-triazine;2-phenyl-p-oxy-4,6-diamino-1,3,5-tri-azine; and2,4,6-triethyl-triamino-1,3,5-triazine. The mono, di-, or tri-arylmelamines, such as 2,4,6-triphenyl-triamino-1,3,5-triazine, arepreferred. Examples of aminoplast resin components are urea, ethyleneurea, thiourea, melamine, benzoguanamine and acetoguanamine. Aldehydesuseful in this invention are formaldehyde, acetaldehyde andpropionaldehyde. The aminoplast resins can be used in the alkylol formbut, preferably, are utilized in the ether form wherein the etherifyingagent is a monohydric alcohol containing from 1 to about 8 carbon atoms.Examples of aminoplast resins are methylol urea, dimethoxymethylol urea,butylated polymeric urea-formaldehyde resins, hexamethoxymethylmelamine, methylated polymeric melamineformaldehyde resin and butylatedpolymeric melamineformaldehyde resin. Other aldehydes used to react withthe amino compound to form the resinous material are crotonic aldehyde,acrolein, or compounds which generate aldehydes, such ashexamethylene-tetramine, paraldehyde, and the like.

A water dispersed coating composition can be prepared by mixing togetheran aqueous dispersion of the in-situ formed epoxy-acrylic copolymer anda water dispersed aminoplast resin. The aminoplast polymer can bedispersed into water by mechanical mixing. The in-situ formed epoxyacrylic copolymer mixture can be prepared in solvent and thensubsequently dispersed into water using a fugitive base such as primary,secondary, and tertiary alkyl, alkanol, aromatic amines, oralkyanolalkyl mixed amines such as monoethanol amine, dimethyl ethanolamine, diethanol amine, triethyl amine, dimethyl aniline, ammoniumhydroxide, and the like, as more particularly described in U.S. Pat. No.4,212,781. The amount of water contained in the coating compositioncontaining the epoxy-acrylic copolymer, and the aminoplast resin dependson the viscosity desired, which in turn, relates to the method ofapplication. For spraying, preferably the coating composition containsbetween about 10% and 30% by weight polymeric solids relative to 70% to90% water including other volatiles such as minor amounts of solvent.For applications other than spraying, the aqueous polymeric dispersionscan contain between about 10% and 40% by weight water. Organic solventscan be utilized to facilitate spray or other application methods andsuch solvents include n-butanol, butyl cellosolve, xylene, toluene, andpreferably n-butanol is used in combination with butyl cellosolve(2-butoxy-ethanol-1). The coating composition of the present inventioncan be pigmented and/or opacified with known pigments and opacifiers.For many uses, including food use, the preferred pigment is titaniumdioxide. The resulting aqueous coating composition can be appliedsatisfactorily by conventional methods known in the coating industry.Thus, spraying, rolling, dipping, and flow coating application methodscan be used for both clear and pigmented films, although spraying ispreferred. After application onto the metal substrate, the coating iscured thermally at temperatures in the range from about 95° C. to about235° C. or higher for time sufficient to effect complete curing as wellas volatilizing of any fugitive component therein.

For metal sheet substrates intended as beverage containers andparticularly for carbonated beverages such as beer, the coating shouldbe applied at a rate in the range from 0.5 to 15 milligrams of polymercoating per square inch of exposed metal surface. To attain theforegoing, the water-dispersible coating as applied can be as thick as0.1 to 1 mil.

For a better understanding of the present invention, the followingexamplesare provided. In this application, all parts are parts byweight, all percentages are weight percentages, and temperatures aredegrees Centigrade unless otherwise specifically noted.

EXAMPLE 1 Phenoxy Grafted Copolymer with 3% MAA

Into a 5 liter, 4-necked round bottom flask was charged 875 g. of butylcellosolve. Through one neck was fitted an air driven mechanicalstirrer, through the second neck was placed a water cooled condenser,through the third neck was placed a thermometer an nitrogen inlet andthrough the fourth neck was placed an addition funnel. The butylcellosolve was heatedto 170° C. with agitation and nitrogen sparge, and1000 g. of phenoxy resin PK HH (from Union Carbide) was slowly added sothat dissolution takes place without lumping. Any water present wasremoved through a trap. After all of the phenoxy resin has dissolved, 25g of volatile was removed through the trap, and 25 g. of butylcellosolve was added back into the reaction flask to replace thevolatile that was removed. The phenoxy resin solution is now cooled to115° C. and 100 g. of n-butanol was then added. Temperature is nowstabilized at 110° C. and a monomer mixture of 37.5 g. of methacrylicacid, 187.5g. of NiBMA (N-isobutoxymethylacrylamide), 12.5 g. ofstyrene, 12.5 g. of ethyl acrylate, 22.1 g. of BPO-78 (Benzoyl Peroxide78% active in water) and 75 g. of butyl cellosolve was added to thephenoxy resin solution in two hours. The reaction mixture was then heldat 110° C. for an hour before its let down into water; 2000 g. ofdeionized water was heatedto 50° C., 30.5 g. of dimethylethanolamine and100 g. of butyl cellosolve were added to the water; 1800 g. of thegrafted phenoxy resin solution was slowly dropped into the agitatedwater-amine solution. A dispersion formed easily. The dispersion had thefollowing constants:

    ______________________________________                                        NV                 24.0%                                                      AN                 26.8 (Acid number)                                         BN                 20.9 (base number)                                         % neutralization   77.8%                                                      ______________________________________                                    

EXAMPLE 2 Phenoxy Grafted Copolymer with 2% MAA

Into a 5 liter 4-necked round bottom flask similarly equipped as inExample1 was charged 875 g. of butyl cellosolve and heating was applied.When the temperature reached 165° C., 1000 g. of phenoxy resin PKHH wasslowly dropped into the butyl cellosolve solution, so that dissolutiontakes place without lumping. Any water present in the phenoxy resin wasstripped off and replaced by butyl cellosolve. After all the phenoxyresinhad dissolved the resin solution was cooled to 120° C. and 100 g.ofn-butanol was added. The temperature is now stabilized at 115° C. anda monomer solution made of the following:

    ______________________________________                                        MAA                   25     g                                                NiBMA                 187    g                                                Styrene               25                                                      Ethylacrylate         12.5                                                    BPO (78)              22.1                                                    Butyl cellosolve      75                                                      ______________________________________                                    

were added to the phenoxy resin solution in two hours and held at 115°C. for 11/2 hours, 1800 g of the grafted copolymer is now dropped into asolution of 2000 g. of deionized water, 27.4 g. of dimethylethanolamineand 100 g. of butyl cellosolve. The temperature of the H₂ O-amine-butylcellosolve solution was 50° C. Initially,the dispersion was grainy,however, after agitation overnight the dispersion became smooth and hadthe bluish color. The dispersion had the following constants:

    ______________________________________                                        NV                    23.1%                                                   AN                    20.2                                                    BN                    20.0                                                    % neutralization      100%                                                    ______________________________________                                    

EXAMPLE 3 Phenoxy Grafted Copolymer with 1% MAA

Into a 5 liter 4-necked round bottom flask similarly equipped as inExample1 was charged 875 g. of butyl cellosolve and heating was applied.When the temperature reached 160° C., 1000 g. of phenoxy resin PKHH wasslowly dropped into the hot butyl cellosolve. When all the phenoxy resindissolved, the solution was cooled to 120° C. and 100 g. of n-butanolwas added. The temperature was now stabilized at 115° C. and a monomersolution made of the following:

    ______________________________________                                        MAA                   12.5   g.                                               NiBMA                 187.5  g.                                               Styrene               25     g.                                               Ethyl acrylate        25     g                                                BPO (78%)             22.1   g.                                               Butyl cellosolve      75     g.                                               ______________________________________                                    

were added to the phenoxy resin solution in two hours. After theaddition of the monomers, the reaction mixture was held at 115° C. for11/2 hours and is now ready to be dropped into water. The drop was donein 2 ways:

    ______________________________________                                        (a)       Resin              1800   g.                                                  Deionized water    2000   g.                                                  Dimethylethanol amine                                                                            10.2   g.                                                  Butyl cellosolve   100    g.                                        ______________________________________                                    

The water-amine-butyl cellosolve was heated to 50° C. before the resinis dropped. The emulsion formed was grainy and 10.2 g. of dimethylethanol amine and 700 g. of deionized water were added. The emulsionbecame less grainy.

    ______________________________________                                                   NV                 24.6%                                                      AN                 14.1                                                       BN                 13.4                                                       % neutralization   95.3%                                           (b)        Resin              200 g.                                                     Deionized water    222 g.                                                     Dimethylethanolamine                                                                              2 g.                                           ______________________________________                                    

The water amine solution was at room temperature. The hot resindispersed into the water-amine solution. The emulsion had small beadspresent which disappeared after further agitation. The NV of theemulsion was 25.6%

EXAMPLE 4 Advanced epoxy resin grafted with 3% MAA

Into a 4-necked 5 liter round bottom flask was charged 1266.4 g. of aliquid epoxy resin DER333 (Dow Chemical Company), 733.6 g. of BisphenolA and 278.4 g. of butyl cellosolve. The reaction mixture was heated to150° C. under 18" Hg vacuum and nitrogen sparge. Heating was stopped andexotherm carried the temperature to 182° C. Vacuum was then turned offand 23.5 g. of volatile was collected. The temperature washeld at 176°C. for 51/2 hours, at the end of the hold, the % oxirane was determinedto be 0.088 and the Gardner-Holt viscosity of the advanced epoxy resinat 40% solids in butyl cellosolve was Z6. 265.2 g. ofbutyl cellsolve wasslowly added to the epoxy resin solution followed by 911.4 g. ofn-butanol.

To 1654 g. of the above epoxy resin solution was added a monomer mixtureconsisted of the following:

    ______________________________________                                        MAA                   34.8   g.                                               Styrene               11.6   g.                                               Ethyl acrylate        11.6   g.                                               NiBMA                 173.8  g.                                               BPO (78%)             20.5   g.                                               Butyl cellosolve      69.5   g.                                               ______________________________________                                    

The epoxy resin solution was at 115° C. The monomer addition took 11/2hour, and the reaction mixture was held at 115° C. for 3 hoursand isthen ready for drop into water. 1652 g. of the resin is slowly droppedinto 2000 g. of deionized water, 40 g. of dimethyl ethanol amine and 100g. of butyl cellosolve. The water solution as heated to 50°C. before theresin dropping. The emulsion formed easily and 100 g. of deionized waterwas then added to the emulsion.

EXAMPLE 5 Advanced epoxy resin grafted with 1% MAA

To 1551 g. of epoxy resin solution prepared in the first paragraph ofExample 4 was added a monomer mixture consisting of

    ______________________________________                                        MAA                   10.9   g.                                               Styrene               21.7   g.                                               Ethyl acrylate        21.7   g.                                               NiBMA                 163    g.                                               BPO (78%)             19.2   g.                                               Butyl cellosolve      65.2   g.                                               ______________________________________                                    

The epoxy resin was heated to 115° C. and the monomer mixture was addedin 2 hours, and the resultant reaction mixture was held for 3 hours at115° C. 1500 g. of the resin was then dropped into a solution at50° C.of

    ______________________________________                                        deionized water        2000   g.                                              dimethylethanol amine  19     g.                                              butyl cellosolve       90     g.                                              ______________________________________                                    

Initially, the resin did not solubilize well. The top liquid phase wasreplaced by deionized water and now the resin dispersed well and formeda smooth emulsion with bluish color.

A sample of the composition disclosed in Example 1 of U.S. Pat. No.4,212,781 was compared with NiBMA grafted phenoxy compositions producedinaccordance with this invention and illustrated in Examples 1-5inclusive. The cured film properties were comparable with respect toporosity, pasteurization, detergent resistance, MEK rubs, andflexibility. However, pine oil absorption of the cured films differedconsiderably as follows:

    ______________________________________                                        Example 1 of U.S. Pat. No. 4,212,781                                                                 1.8 mg absorption                                      Examples 1-5 inclusive 0.5 mg. absorption                                     ______________________________________                                    

Pine oil is a severe test based on the fact that limonene is present insome soft drinks, as well as pine oil. The test panels containing curedpaint films were exposed to pine oil vapors in closed containers for 3days. The weight pick-up on the test panels (foil) indicates theabsorption. The cured paint films of Examples 1-5 indicate improvedbarrier properties and a superior interior can coating.

In accordance with the invention, all of these grafted copolymers withlow acid number (below 30) have self-curing capability as well ascurable withother crosslinkers such as melamine resin, urea resins,phenolic resins, epoxy resins diisocyanates etc. Due to the low acidnumber, the coatings made from these grafted copolymers have excellentproperties, e.g., salt spray, detergent resistance etc., as well assuperior resistance to pine oil. They also have excellent adhesion tovarious substrates and are extremely tough.

The merits of the invention are illustrated by the foregoing descriptionand illustrative examples, but are not intended to limit except as bythe appended claims.

We claim:
 1. A self-curing epoxy-acrylic graft copolymer comprisingunsaturated monomer chains grafted by carbon-to-carbon graft to theepoxy resin backbone by in-situ copolymerization of said monomers in thepresence of said epoxy resin, said epoxy resin being a phenoxyterminated epoxy comprising excess equivalents of bisphenol reacted withlesser equivalents of epoxide and having a number average molecularweight between 4,000 and 40,000, the ethylenically unsaturated monomerscomprising between 1% and 25% by weight alkylated alkylol acrylamidemonomer and the remaining being other ethylenic monomers includingfunctional monomer, said graft copolymer produced in the absence ofwater by in-situ polymerization of said ethylenically unsaturatedmonomers in the presence of at least 3% by weight of peroxide initiatorbased on the weight of said ethylenically unsaturated monomerscopolymerized, the polymerized monomers comprising between 10 and 100weight parts per 100 weight parts of epoxy resin, where the Acid No. ofthe epoxy-acrylic graft copolymer is below 30, and said epoxy-acrylicgraft copolymer is dispersed into water by adding amine and water to theepoxy-acrylic graft copolymer.
 2. The composition in claim 1 wherein thein-situ polymerization of monomers is in the presence of organic solventto produce a solvent dispersed epoxy-acrylic graft copolymer beforedispersing into water.
 3. The composition in claim 1 wherein the in-situpolymerization is in the absence of organic solvent and theepoxy-acrylic graft copolymer is subsequently dispersed into organicsolvent before dispersing into water.
 4. The composition in claim 1wherein the epoxy-acrylic graft copolymer comprises carbon to carbongraft epoxy-acrylic copolymer, ungrafted acrylic copolymer, andungrafted epoxy resin.
 5. The composition in claim 1 wherein thepolymerized ethylenically unsaturated monomers include carboxylmonomers.
 6. The composition in claim 5 wherein the carboxyl monomerscomprise between 1% and 35% of the ethylenically unsaturated monomer. 7.The composition in claim 1 where the phenoxy terminated epoxy resincomprises a substantially linear polymer characterized by the generalformula: ##STR2## where n is between 30 and
 80. 8. In a process forproducing a self-curing epoxyacrylic graft copolymer by in-situcopolymerization of ethylenically unsaturated monomers in the presenceof epoxy resin, the improvement comprising:providing a phenoxyterminated epoxy resin having a number average molecular weight between4,000 and 40,000 and produced by reacting excess equivalents ofbisphenol with lesser equivalents of epoxide; copolymerizingethylenically unsaturated monomers in the presence of said epoxy resinand in the absence of water to provide a carbon-to-carbon graft of saidmonomers to said epoxy resin backbone, the ethylenically unsaturatedmonomers comprising between 1% and 25% by weight alkylol acrylamidemonomer and other ethylenically unsaturated monomer including functionalmonomer, said monomers copolymerized in the presence of at least 3% byweight peroxide initiator based on the weight of said monomers, wherethe copolymerized monomers comprise by weight between 10 and 100 weightparts per 100 weight parts of epoxy-resin, to produce an epoxy-acrylicgraft copolymer having an Acid No. below 30; and dispersing saidepoxy-acrylic graft copolymer into water by adding amine and water tothe epoxy-acrylic graft copolymer.
 9. The process in claim 8 where thephenoxy terminated epoxy resin is produced by reacting a low molecularweight liquid epoxy resin with excess equivalents of bisphenol-A. 10.The process in claim 8 where the phenoxy terminated epoxy resin isproduced by reacting excess equivalents of bisphenol-A with lesserepoxide equivalents of bisglycidyl ether of bisphenol-A.
 11. The processin claim 8 where the epoxy resin is dispersed into solvent prior tocopolymerizing said monomers in the presence of the epoxy resin.
 12. Theprocess in claim 8 where the ethylenically unsaturated monomers includebetween 1% and 35% by weight carboxyl monomers based on the total weightof ethylenically unsaturated monomers copolymerized.